CN1764001A - Polymer electrolyte for a direct oxidation fuel cell, method of preparing the same, and direct oxidation fuel cell comprising the same - Google Patents
Polymer electrolyte for a direct oxidation fuel cell, method of preparing the same, and direct oxidation fuel cell comprising the same Download PDFInfo
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- CN1764001A CN1764001A CNA2005101137233A CN200510113723A CN1764001A CN 1764001 A CN1764001 A CN 1764001A CN A2005101137233 A CNA2005101137233 A CN A2005101137233A CN 200510113723 A CN200510113723 A CN 200510113723A CN 1764001 A CN1764001 A CN 1764001A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
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- H—ELECTRICITY
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
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Abstract
A polymer electrolyte membrane for a direct oxidation fuel cell includes a porous polymer supporter having a plurality of pores, and a hydrocarbon fuel diffusion barrier layer which is formed on the polymer supporter and contains an inorganic additive dispersed in a cation exchange resin.
Description
Technical field
The present invention relates to a kind of polyelectrolyte film that is used for direct oxidation fuel cell, and preparation method thereof, and a kind of direct oxidation fuel cell system that comprises it.More specifically, the present invention relates to a kind of direct oxidation fuel cell system with high power density, it utilizes film to prevent the infiltration of hydrocarbon fuel.
Background technology
Fuel cell is the electrochemical redox reaction by the hydrogen in oxidant and hydrocarbon-Ji material such as methyl alcohol, ethanol or the natural gas, produces the electricity generation system of electric energy.
The general example of fuel cell is polyelectrolyte film fuel cell (PEMFC) and direct oxidation fuel cell (DOFC).The direct oxidation fuel cell of utilizing methyl alcohol to act as a fuel is called as direct methanol fuel cell (DMFC).The polyelectrolyte film fuel cell is the eco-friendly energy, and it can replace fossil fuel energy.It has many advantages, as the high power output density, and high-energy conversion efficiency, operability at room temperature, and can reduce size and closely sealing.Therefore, it can be widely used in various fields such as pollution-free automobile, the household system, and be used for the compact power of mobile communication equipment and military equipment.
The polyelectrolyte film fuel cell has the high advantage of energy density, but problem is also arranged, and promptly needs handled hydrogen, perhaps need auxiliary device as be used to reform combustion gas such as methane, methyl alcohol or natural gas to produce the fuel reforming processor of required hydrogen.
On the contrary, the energy density of direct oxidation fuel cell is generally low than polymer electrolyte fuel cell, but has following advantage: easy treat liquid kind of fuel, working temperature is low, and does not need other fuel reforming processor.Therefore, this direct oxidation fuel cell can be to be used for small-sized and the appropriate system general objects compact power.
In fuel cell, the battery pack of actual power comprises several element cells to tens multiple-level stacks, and each element cell all is made up of membrane-electrode assembly (MEA) and dividing plate (being also referred to as bipolar plates).Membrane-electrode assembly has by separate anode of electrolyte membrane (being called fuel electrode or oxidizing electrode) and negative electrode (being called air electrode or reducing electrode).
Often perfluorinated sulfonic resin film (NAFION
) being used for polyelectrolyte film, it has good electrical conductivity, mechanical property and chemical resistance.
Usually, thicker perfluorinated sulfonic resin film provides better dimensional stability and mechanical property, but has increased film resistor.Thin film provides lower film resistor, but has provided relatively poor mechanical property, and unreacted thus fuel gas and liquid is often by polymer film, and causes the loss and the battery performance of unreacted fuel in the course of the work lower.
Particularly, with the polyelectrolyte film of platinum catalyst electrode hot pressing,, and utilize 3～50wt% methanol fuel to cause maximum 200% the change in volume that surpasses along with the degree of temperature and hydration stands 15～30% variation of film thickness and volume.Because this swelling of electrolyte membrane causes the thickness increase and applies pressure on the gas diffusion layers that this gas diffusion layers is an electrode basement.When the fuel cell long-term work, the surface size of film changes and causes the physical deterioration (physicaldeterioration) at the interface between catalyst granules and the electrolyte membrane.
Summary of the invention
First embodiment of the invention provides a kind of polyelectrolyte film that is used for direct oxidation fuel cell, and it has good electrochemical properties, thermal stability, dimensional stability and mechanical characteristics, and the infiltration of the hydrocarbon fuel that reduces.
Second embodiment of the invention provides a kind of preparation to be used for the method for the polyelectrolyte film of direct oxidation fuel cell.
Third embodiment of the invention provides a kind of membrane-electrode assembly, and it comprises described polyelectrolyte film.
Four embodiment of the invention provides a kind of direct oxidation fuel cell, and it comprises described membrane-electrode assembly.
According to first embodiment of the invention, a kind of polyelectrolyte film that is used for direct oxidation fuel cell comprises the porous polymer carrier with a lot of holes, and is formed on the hydrocarbon fuel diffusion impervious layer on this polymer support.Described hydrocarbon fuel diffusion impervious layer comprises cation exchange resin and the inorganic additive (inorganic filler) that is dispersed in this cation exchange resin.
By the embedding of cation exchange resin chain, the inorganic additive in the cation exchange resin can be layered as the nanophase shape.
The limiting examples of inorganic additive comprises and is selected from least a in following or two or more mixture: silica, aluminium oxide, zeolite, barium titanate, pottery, inorganic silicate, phosphoric acid hydrogen zirconium, α-Zr (O
A1PCH
A2OH)
a(O
B1PC
B2Hb4SOb
5H)
bNH
2O (a1, a2, a, b1, b2, b4, b5 and b are same to each other or different to each other in the formula, and are 0～14 integer, and n is 0～50 integer), v-Zr (PO
A1) (H
A2PO
A3)
a(HO
B1PC
B2H
B3SO
B4H)
bNH
2O (a1, a2, a3, a, b1, b2, b3, b4 and b are same to each other or different to each other in the formula, and are 0～14 integer, and n is 0～50 integer), Zr (O
A1PC
A2H
A3)
aY
b(a1, a2, a3, a and b are same to each other or different to each other in the formula, and are 0～14 integer), Zr (O
A1PCH
A2OH)
aY
bNH
2O (a1, a2, a and b are same to each other or different to each other in the formula, and are 0～14 integer, and n is 0～50 integer), α-Zr (O
A1PC
A2H
A3SO
A4H)
aNH
2O (a1, a2, a3, a4 and a are same to each other or different to each other in the formula, and are 0～14 integer, and n is 0～50 integer), α-Zr (O
A1POH) H
2O (a1 is 0～14 integer in the formula), (P
2O
5)
a(ZrO
2)
bGlass (a and b are same to each other or different to each other in the formula, and are 0～14 integer), P
2O
5-ZrO
2-SiO
2Glass and composition thereof.In one embodiment, inorganic silicate is most preferred.
Described silicate has sheet shape hierarchy and comprises pyrophyllite (pyrophylite)-talcum, montmorillonite (MMT), fluorine hectorite (fluorohectorite), kaolinite, vermiculite, illite, mica or clintonite.Silicate is dispersed in the cation exchange resin with nanophase, thereby makes the silicate layering between the silicate plate with polymer chain embedding dispersion.
The aspect ratio of inorganic silicate is preferably 1/30～1/1000, and long axis length is 0.05～0.5 μ m.When making inorganic silicate in cation exchange resin during layering, the distance between each silicate layer is preferred minimum to be 3nm.Distance when the silicate layer spacing is defined as in polymer chain being embedded sheet phase silicate between each layer of layering and in one embodiment, minimum is 3nm.When more polymer chain embedding and interfloor distance increase, then silicate layer disperses disorderly, so that term " interfloor distance " is no longer suitable, measures because be difficult to.Thereby to specify interfloor distance minimum be that 3nm is enough, and when interlamellar spacing was maximum, each layer disperses so disorderly so that energy measurement should distance.
In one embodiment, the preferred thickness of polymer film is 5～100 μ m.
In one embodiment, the preferred thickness of polymer support is 10～15 μ m, and the preferred thickness of hydrocarbon fuel diffusion impervious layer is 2～10 μ m.
According to second embodiment of the invention, a kind of method for preparing polyelectrolyte film comprises: obtain mixed solution by mixed-cation exchanger resin liquid and solid phase or liquid phase inorganic additive, make polymer film thereby this mixed solution is coated on the porous polymer carrier.The cation exchange resin of the side chain by will having cation exchange group is dissolved in first organic solvent, makes described cation exchange resin liquid.
According to an embodiment of the invention, described first organic solvent is selected from: N-N-methyl-2-2-pyrrolidone N-(NMP), dimethyl formamide (DMF), dimethylacetylamide (DMA), oxolane (THF), methyl-sulfoxide (DMSO), acetone, methylethylketone (MEK), tetramethylurea, trimethyl phosphate, butyrolactone, isophorone, carbitol acetate, methylisobutylketone, N-butylacetic acid ester, cyclohexanone, diacetone alcohol, isobutyrone, ethyl acetoacetate, glycol ether, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and composition thereof.
In one embodiment, the cation exchange resin liquid based on 100 weight portions preferably is blended in the inorganic additive of 0.5～10 weight portion in the mixed solution.
According to third embodiment of the invention, a kind of membrane-electrode assembly of fuel cell is provided, it comprises above-mentioned polyelectrolyte film.
According to four embodiment of the invention, a kind of fuel cell comprises above-mentioned membrane-electrode assembly.
Description of drawings
Figure 1A is a polyelectrolyte film of the present invention;
Figure 1B is the structure chart that is used for the present invention's inorganic silicate;
Fig. 1 C is a membrane-electrode assembly of the present invention;
Fig. 2 is the structural representation of direct oxidation fuel cell of the present invention system;
Fig. 3 is the SEM photo according to (mapped) polyelectrolyte film of the A1-mapping of embodiments of the invention 1;
Fig. 4 is the SEM photo according to the polyelectrolyte film of the A1-mapping of Comparative Examples 1;
Fig. 5 be according to the polyelectrolyte film of embodiments of the invention 1 and Comparative Examples 1 and 3 along with the change in volume of the methanol concentration that changes than figure;
Fig. 6 is the profile morphology figure according to the polyelectrolyte film of embodiments of the invention 1;
Fig. 7 is the profile morphology figure according to the polyelectrolyte film of Comparative Examples 1;
Fig. 8 is the power output density figure according to the fuel cell of embodiments of the invention 1;
Fig. 9 is the power output stability figure according to the fuel cell of embodiments of the invention 1 and Comparative Examples 3; And
Figure 10 is the transmission electron micrograph according to the polyelectrolyte film of embodiments of the invention 2.
Embodiment
With reference to Figure 1A, the present invention relates to a kind of polyelectrolyte film 14 that is used for direct oxidation fuel cell, this polyelectrolyte film comprises porous polymer carrier 10 and the hydrocarbon fuel diffusion impervious layer 12 that is formed on this polymer support.
This hydrocarbon fuel diffusion impervious layer comprises the inorganic additive that is dispersed in the cation exchange resin.In the present invention, term " fuel " is meant gas or liquid hydrocarbon fuel, and its general example comprises methyl alcohol, ethanol, propyl alcohol, butanols and natural gas.
Though the thickness of polyelectrolyte film is 5～100 μ m, be preferably 5～50 μ m, but carrier the dimensional stability of polyelectrolyte film be can improve, the expansion or the contraction of moisture prevented to rely on, keep electrode-electric to separate the physical property at liquid interface, and prolong the life-span of fuel cell.The present invention can help avoid and use the thick perfluoro sulfonic acid membrane of 130～180 μ m in direct oxidation fuel cell, and it has increased film resistor.According to the present invention, can reduce the thickness and the film resistor of polyelectrolyte film, cause being used for the fuel cell system of the smaller szie of small portable electronic device such as mobile phone.
Korean patent application 2004-51287,2003-45234 and 2004-47240 disclose the polyelectrolyte film that utilizes inorganic additive.Yet disclosed in the prior art polyelectrolyte film does not utilize the porous polymer carrier, therefore, can be mechanically too frangible as the film that the about 30 μ m among the present invention are thick, hydrogen permeable, and can show the excessive penetration that hydrocarbon fuel such as methyl alcohol are arranged.The present inventor finds unexpectedly, by comprising polymer support, the film with good intensity and durability can be provided, and not allow excessive fuel infiltration.
The porous polymer carrier comprises and is selected from following material: the homopolymers of polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyimides, polybenzoxazole and polybenzimidazoles, and copolymer.Cation exchange resin comprises the homopolymers of fluoro-base resin, and in order to adhere at the interface of improving between polymer support and the cation exchange resin, the preferred material of porous polymer carrier comprises polytetrafluoroethylene, polyvinylidene fluoride or its copolymer.For this embodiment, the polytetrafluoroethylene homopolymers is most preferred.
Described cation exchange resin comprises fluoropolymer resin, and this fluoropolymer resin comprises as the following cation exchange group of being selected from of side chain: sulfonic group, carboxylic acid group, phosphate, phosphonate group, and derivative.
The limiting examples of cation exchange resin comprises at least a protonically conductive polymer that is selected from following: the fluoro-based polyalcohol, benzimidazole-based polyalcohol, polyimides-based polyalcohol, Polyetherimide-based polyalcohol, polyphenylene sulfide-based polyalcohol, polysulfones-based polyalcohol, polyether sulfone-based polyalcohol, polyether-ketone-based polyalcohol, polyethers-ether ketone-based polyalcohol, and polyphenylene quinoxaline-based polyalcohol.Preferred proton-conducting polymer comprises fluoro-based polyalcohol, polybenzimidazoles-based polyalcohol and polysulfones-based polyalcohol.
The instantiation of fluoro-based polyalcohol comprises poly-(perfluorinated sulfonic acid) (NAFION of following formula 1
, E.I.Dupont de Nemours Company), below the Aciplex of formula 2
TM(Asahi Kasei Chemical), Flemion
TM(Asahi Glass) and Fumion
TMThe vinethene fluoride of (commercial is Fumatech) carbon fluroxene or following formula 3.Can also use the various polymer that are disclosed in US 4330654,4358545,4417969,4610762,4433082,5094995,5596676 and 4940525.
Wherein in following formula 1, X is H, Li, Na, K, Cs, 4-butyl amine or NR1R2R3R4, and R1, R2, R3 and R4 are independently selected from H, CH in the formula
3And C
2H
5, m is at least 1, and n is at least 2, and x is about 3.5～5, and y is at least 1000.
MSO
2CFRfCF
2O[CFYCF
2O]
nCF＝CF
2 (2)
Wherein in formula 2, Rf is fluorine or C
1～C
10Perfluoroalkyl, Y are fluorine or trifluoromethyl, and n is 1～3, and M is selected from: fluorine, hydroxyl, amino and-OMe (in the formula, Me is alkali metal base or quaternary ammonium group).
Wherein in formula 3, k is 0 or 1, and l is 3～5 integer.
With above-mentioned perfluorinated sulfonic acid (NAFION
) the hydration of sulfonic acid end group form micellar structure, its provide the protolysis passage and as acidic aqueous solution equally work.In the present invention, when using perfluorinated sulfonic acid (NAFION
) during as cation exchange resin, the ion-exchange group (SO of side chain terminal
3X) X in can replace with monovalent ion such as hydrogen ion, sodium ion, potassium ion, cesium ion or TBuA.
Poly-(ether ether ketone) that the instantiation of benzimidazole-based polyalcohol, polyimides-based polyalcohol, Polyetherimide-based polyalcohol, polyphenylene sulfide-based polyalcohol, polysulfones-based polyalcohol, polyether sulfone-based polyalcohol, polyether-ketone-based polyalcohol, polyethers-ether ketone-based polyalcohol and polyphenylene quinoxaline-based polyalcohol comprises polybenzimidazoles, polyimides, polysulfones, polysulfones derivative, sulfonation (s-PEEK), polyphenylene oxide, polyphenylene sulfide and polyphosphazene (polyphosphazane).
As selection, can use polystyrolsulfon acid polymer wherein to be grafted to electrolyte membrane on polyethylene, polyacrylic polymer, fluoroethylene polymer or the ethylene/tetrafluoroethylene polymer.
Can adjust the proton-conducting of cation exchange resin by equivalent.Simultaneously, definition " ion exchange ratio of ion exchange resin " is determined by carbon number in main polymer chain and cation exchange group number.According to an embodiment of the invention, ion exchange ratio is 3～33.This is corresponding to about 700～2000 equivalent weight (EW).
During the equivalent weight value is interpreted as and the weight of the required acidic polymer of the alkali (NaOH) of 1 equivalent.When equivalent weight was very big, resistance increased, and when it very hour, its mechanical property worsens.Therefore, need the control equivalent weight in proper range so that the enough low resistance and the mechanical property of abundance to be provided.
Inorganic additive has increased mechanical strength and has reduced hydrocarbon fuel such as methanol permeation.The limiting examples of inorganic additive comprises and is selected from following material: silica (for example, fumed silica, silica gel, Cab-O-Sil
TM), aluminium oxide, mica, zeolite (SAPO-5
TM, XSM-5
TM, AIPO-5
TM, VPI-5
TM, MCM-41
TMDeng), barium titanate, pottery, inorganic silicate, phosphoric acid hydrogen zirconium, α-Zr (O
A1PCH
A2OH)
a(O
B1PC
B2H
B4SO
B5H)
bNH
2O (a1, a2, a, b1, b2, b4, b5 and b are same to each other or different to each other in the formula, and are 0～14 integer, and n is 0～50 integer), v-Zr (PO
A1) (H
A2PO
A3)
a(HO
B1PC
B2H
B3SO
B4H)
bNH
2O (a1, a2, a3, a, b1, b2, b3, b4 and b are same to each other or different to each other in the formula, and are 0～14 integer, and n is 0～50 integer), Zr (O
A1PC
A2H
A3)
aY
b(a1, a2, a3, a and b are same to each other or different to each other in the formula, and are 0～14 integer), Zr (O
A1PCH
A2OH)
aY
bNH
2O (a1, a2, a and b are same to each other or different to each other in the formula, and are 0～14 integer, and n is 0～50 integer), α-Zr (O
A1PC
A2H
A3SO
A4H)
aNH
2O (a1, a2, a3, a4 and a are same to each other or different to each other in the formula, and are 0～14 integer, and n is 0～50 integer), α-Zr (O
A1POH) H
2O (a1 is 0～14 integer in the formula), (P
2O
5)
a(ZrO
2)
bGlass (a and b are same to each other or different to each other in the formula, and are 0～14 integer), P
2O
5-ZrO
2-SiO
2Glass, and composition thereof.Inorganic silicate is preferred inorganic additive.
According to an embodiment, inorganic silicate is a clay, that is, and and the silicate of general most of layering.As shown in Figure 1, its basic structure is made up of the combination of silicon-oxygen tetrahedron sheet and alumina octahedra sheet, and is the hierarchy that forms by above-mentioned two hydroxyl condensation reaction.
According to their negative charge amount, silicate can be divided into pyrophyllite-talcum, montmorillonite (MMT), fluorine hectorite, kaolinite, vermiculite, illite, mica or clintonite, and any may be used among the present invention in these materials.In one embodiment of the invention, preferred montmorillonite.
In the structure of montmorillonite, the Al in the alumina octahedra sheet
3+Ion is used Mg
2+, Fe
2+Or Fe
3+Ion replaces, and the Si in the silicate tetrahedral sheet
4+Ion is used Al
3+Ion replaces, and montmorillonite integral body has negative electrical charge.And, in order to keep the total charge balance, between each layer of silicate, comprise tradable cation and hydrone.
In one embodiment, the aspect ratio of silicate is 1/30～1/1000, is preferably 1/100～1/800, more preferably 1/500～1/800.When the aspect ratio of silicate was lower than 1/30, the silicate of layering can not serve as the diffusion impervious layer of gas and liquid, and its barrier properties worsens.When the aspect ratio of silicate greater than 1/1000 the time, be difficult to cause layering that silicate is not dispersed in the cation exchange resin in the polyelectrolyte film as a result by the embedding of cation exchange resin chain.
In one embodiment, the long axis length of silicate is 0.05～0.5 μ m, is preferably 0.05～0.2 μ m.When long axis length was lower than 0.05 μ m, the blocking effect to hydrocarbon fuel that does not form sheet-shape structure and it descended, and when it during greater than 0.5 μ m, it is difficult to be distributed in the hole of carrier.
Distance when the silicate interfloor distance is meant in polymer chain being embedded sheet phase silicate between each layer of layering.In one embodiment, when making inorganic silicate in cation exchange resin during layering, the silicate interfloor distance is preferred minimum to be 3nm.When heteropolymer chain more embeds and interfloor distance when increasing, silicate layer disperses disorderly, so that energy measurement interfloor distance not.Thereby to specify interfloor distance minimum be that 3nm is enough, because specified maximums is nonsensical.
Silicate can be handled with organic modifiers.Strong Van der Waals gravitation makes sheet-shape silicate be difficult to layering and is dispersed in the fluoropolymer resin, but cause it to be penetrated between each sheet with low-molecular-weight organic modifiers processing, promote the embedding of fluoropolymer resin, thereby promoted layering and dispersion.
Suitable organic modifiers can comprise C1～C20 alkylamine, C1～C20 Alkylenediamine, C1～C20 quaternary ammonium salt, aminohexane and nitrogenous heterocyclic compound.
The instantiation of alkylamine comprises methylamine hydrochloride, propylamine, butylamine, octylame, decyl amine, lauryl amine, cetylamine, octadecylamine, and N-methyl octadecylamine.
The limiting examples of Alkylenediamine comprises 1, the 6-hexamethylene diamine, and 1,12-dodecyl diamines.
The limiting examples of quaternary ammonium salt comprises the dimethyl quaternary ammonium, benzyl quaternary ammonium, 2-second hexyl quaternary ammonium, two-2-ethoxy quaternary ammonium, methyl quaternary ammonium, tetramethyl ammonium chloride, octadecyl trimethyl ammonium bromide, the bromination dodecyl trimethyl ammonium, the two octadecyl Dimethyl Ammonium of bromination, and two (2-ethoxy) the methyl octadecyl ammonium of chlorination.
The limiting examples of aminohexane comprises the 6-aminohexane, and the 12-aminohexane.The limiting examples of nitrogenous heterocyclic compound is a chlorination 1-cetyl pyridinium.
As mentioned above, back use inorganic silicate can handled with organic modifiers.As selection, can use the inorganic silicate of organic improving.Suitable organically-modified inorganic silicate comprises Cloisite6A, Cloisite10A, Cloisite15A, Cloisite20A, Cloisite25A and the Cloisite30B that is produced by Southern Clay Products.In one embodiment, preferred Cloisite10A.
In one embodiment, cation exchange resin and inorganic additive all both be present in the hole, were present in again on the surface of polymer support.In another embodiment, cation exchange resin not only is present in the hole but also be present on the surface of polymer support, and inorganic additive exists only on the surface of polymer support.
In one embodiment, the porosity of polymer support is 80% or bigger, is preferably 80～90%.When the porosity of polymer support was lower than 80%, the weight of non-conducting polymer was too high and cause that the conductivity of composite membrane reduces.80～90% porosity is suitable for forming the continuous process of film, because it can improve the mechanical characteristics of carrier.
In one embodiment, between the surface and apparent surface of polyelectrolyte film, that is, the electric conductivity difference that forms thereon between two surfaces of catalyst layer is 5% or littler, is preferably 3～5%.Because determined its film resistor on the lower surface of relative conductivity of the thickness direction of polyelectrolyte film, so preferred electric conductivity difference is 5% or lower, so that promote electron conduction.
In one embodiment of the invention, the porosity of polyelectrolyte film is 1～10%, more preferably 1～5%.
The carrier thickness of polyelectrolyte film of the present invention can be 10～15 μ m, and hydrocarbon fuel diffusion barrier layer thickness can be 2～10 μ m.When the thickness of hydrocarbon fuel diffusion impervious layer was in above-mentioned scope, then the surface roughness of electrolyte membrane increased and the effective surface area of its per unit area increases, thereby increases the contact area between catalyst and the electrolyte membrane.When the thickness of hydrocarbon fuel diffusion impervious layer surpassed 10 μ m, then blocking effect improved, but its surface becomes smooth and can not obtain to increase the effect of contact area between catalyst and the electrolyte membrane.When its thickness was lower than 2 μ m, then contact area increased, but blocking effect reduces.
Polyelectrolyte film comprises the inorganic additive with hierarchy, and its embedding by the cation exchange resin chain is layered as nanophase.Additive has prolonged liquid or the gas phase fuel passage by it, therefore plays a part liquid fuel is stopped.The extremely thin film that contains polymer support can improve the dimensional stability and the mechanical property of polyelectrolyte film.
According to embodiment of the present invention, the amount of the cation exchange resin of polyelectrolyte film is 50～90wt%, and the amount of porous polymer carrier is 2～30wt%, and the amount of inorganic additive is 0.5～20wt%.In another embodiment, the amount of cation exchange resin is 70～80wt%, and the amount of porous polymer carrier is 2～15wt%, and the amount of inorganic additive is 0.5～10wt%.When the amount of porous polymer carrier and inorganic additive is higher than above-mentioned scope because two kinds of materials all right and wrong are conductive, so the conductivity of film reduces.When they were lower than above-mentioned scope, mechanical strength and dimensional stability worsened and do not obtain required blocking effect for hydrocarbon fuel fully.
According to the present invention, the hydrocarbon fuel diffusion impervious layer can also comprise and has low-molecular-weight acrylate-based polyalcohol.The limiting examples of acrylate-based polyalcohol comprises that molecular weight is lower than 1000 polyethyleneglycol diacrylate and polyethylene glycol dimethacrylate.This low-molecular-weight acrylate-based polyalcohol embeds in the inorganic additive easily and helps the layering of activated inorganic additive.In one embodiment, based on the cation exchange resin of 100 weight portions, comprise 5～10 parts by weight of acrylic ester-based polyalcohols.
Hereinafter, will the method that prepare polyelectrolyte film be described in more detail.
At first, by mixed-cation exchanger resin liquid and solid phase or liquid phase inorganic additive, make mixed solution.The cation exchange resin of the side chain by will having cation exchange group is dissolved in first organic solvent, makes cation exchange resin liquid.
In mixed process, the cation exchange resin chain is embedded between the multilayer inorganic additive, inorganic additive is layered as the nano-scale sheet.When utilizing this formulations prepared from solutions electrolyte membrane, electrolyte membrane comprises the sheet-shape inorganic additive that is dispersed in the cation exchange resin, improving the mechanical property of polyelectrolyte film greatly, and prolong liquid phase or gas phase fuel passage, thereby reduce fuel permeability by polyelectrolyte film.
During the nano-scale sheet layering of inorganic additive, the contact area between organic polymer and the inorganic additive increases, and therefore strengthens molecular attraction and mechanical property in polyelectrolyte film.Played a part to stop fuel infiltration by the additive of layering, thereby significantly reduce the infiltration of gas or liquid hydrocarbon fuel.
Be dissolved in by cation exchange resin in first organic solvent of 100 weight portions, make cation exchange resin liquid 1～10 weight portion.When the amount of the cation exchange resin that uses was lower than 1 weight portion, then cation exchange resin embedded between the multilayer inorganic additive easily, but needed longer time drying and its viscosity lower, made more to be difficult to be coated on the porous polymer carrier.When the amount of using during, then need the long time to be embedded between the multilayer inorganic additive greater than 10 weight portions.
In said process,, as be 5wt%NAFION when the commercial cation exchange resin that obtains of use predissolve in solvent
/ H
2Perfluorinated sulfonic acid (the NAFION of O/2-propanol solution
) time, at room temperature dry to remove H fully
2O/2-propyl alcohol solvent, then be dissolved in it in the organic solvent once more after, can use it.
Under 90～120 ℃, stir and finished course of dissolution in 6～72 hours.
The limiting examples of described first organic solvent comprises N-N-methyl-2-2-pyrrolidone N-(NMP), dimethyl formamide (DMF), dimethylacetylamide (DMA), oxolane (THF), methyl-sulfoxide (DMSO), acetone, methylethylketone (MEK), tetramethylurea, trimethyl phosphate, butyrolactone, isophorone, carbitol acetate, methylisobutylketone, N-butylacetic acid ester, cyclohexanone, diacetone alcohol, isobutyrone, ethyl acetoacetate, glycol ether, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate), and composition thereof.
By inorganic additive being dispersed in second organic solvent, can use original solid-state or liquid inorganic additive.In this manual, inorganic additive liquid is included in the inorganic additive of any state in the liquid organic solvent, and can comprise suspension or dispersion, but is not limited thereto.
When using liquid inorganic additive, make inorganic additive liquid in second organic solvent thereby inorganic additive joined.The suitable solvent of second organic solvent comprises 1-propyl alcohol, 2-propyl alcohol or its mixture.
Can mixed-cation exchanger resin liquid and inorganic additive, so that inorganic additive is 0.5～10 weight portion based on the cation exchange resin liquid of 100 weight portions.When inorganic additive was lower than 0.5 weight portion, dispersion reduced, and it increases the infiltration of hydrocarbon fuel.When it during greater than 10 weight portions, then excessive inorganic additive is dispersed in the cation exchange resin of the polyelectrolyte film that makes, and sheet-shape inorganic additive layering and mechanical strength are weakened.
Low molecular weight propylene acid esters-based polyalcohol can also be joined in the mixed solution.Usually use liquid low molecular weight propylene acid esters-based polyalcohol.Based on the cation exchange resin of 100 weight portions, can add 5～10 parts by weight of acrylic ester-based polyalcohols.
Resulting mixed solution is coated on the polymer support, makes polyelectrolyte film.Can utilize any method to finish coating, but being coated with the number of plies is important for obtaining effect required for the present invention fully.In one embodiment, in order to obtain the uniform ion conductivity of polyelectrolyte film, coating is carried out twice or repeatedly.Preferred coating three to five times.The amount of used coating liquid can in one embodiment, can be utilized 1g mixed solution coating 200cm according to the thickness adjusted of polymer support film in the coating
2Thickness is the polymer support of 50 μ m, but can use excessive a little coating liquid always.
When only finishing when once being coated with, perhaps when watering mixed solution in the polyelectrolyte film, do not have the hole of complete closed carrier, thereby cause uneven ionic conductivity.
And, utilize the both sides of described coating process coated polymeric carrier normally more effective.The thickness of polyelectrolyte film is 5～100 μ m.In one embodiment, in order to obtain so thick polyelectrolyte film, should be dry under 100 ℃ or higher temperature after the coating.
Before being coated on mixed solution on the polymer support, can be on this polymer support with the pre-coating of cation exchange resin liquid.By pre-coating, polyelectrolyte film only comprises cation exchange resin in the hole in polymer support, therefore with cation exchange resin complete closed hole.Then cation exchange resin and inorganic additive are applied on the surface of polymer support, thereby form the hydrocarbon fuel diffusion impervious layer.In this process, the thickness of hydrocarbon fuel diffusion impervious layer is less than or equal to 1/3 of polymer support.
In coating process, after carbon paper is placed on the both sides of polymer support, with mixed solution be coated in the porousness substrate, rolling and dry.Can repeat this process, remove the porousness carbon paper then.By capillarity mixed solution is immersed in the hole of carrier equably, then evaporating solvent.Thereby the hole of carrier can be by the inorganic additive of layering and cation exchange resin complete closed.
The thickness that utilizes the conventional polymer electrolyte membrane of perfluorinated sulfonic acid is 130～180 μ m, so that suppress the infiltration of hydrocarbon fuel.Along with thickness increases, proton-conducting reduces and the cost of polyelectrolyte film increases.Even be 5～100 μ m, be preferably the extremely thin polymer film of 5～50 μ m for thickness, polyelectrolyte film of the present invention also can improve mechanical property greatly, and reduces the sheet-shape inorganic additive of hydrocarbon fuel infiltration by polymer support and nano-scale.
The inorganic additive that is dispersed in the resin of polyelectrolyte film has prolonged the diffusion admittance of hydrocarbon fuel, thereby reduces the infiltration of hydrocarbon fuel.Thickness is the blocking effect of the extremely thin film of the present invention of 5～100 μ m for hydrocarbon fuel, and the polyelectrolyte film thick with 180 μ m is identical or better than it.Film of the present invention can be used for preparing high power density fuel cell.And it is simple and be suitable for large-scale production to prepare the method for polyelectrolyte film.
Shown in Fig. 1 C, polyelectrolyte film 14 of the present invention is placed between negative electrode 16 and the anode 18, constitute membrane-electrode assembly 51.
Negative electrode and anode comprise electrode basement and catalyst layer.
The catalyst layer of electrode comprises metallic catalyst, and it promotes correlated response, that is, and and the reduction of fuel oxidation and oxidant.Suitable catalyst comprises and is selected from following metal: platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palldium alloy, platinum-M alloy, and composition thereof, wherein M is at least a transition metal that is selected from following: Ga, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn.Preferred catalyst comprises and is selected from following metal: platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palldium alloy, platinum-cobalt alloy and platinum-nickel alloy.
Usually, metallic catalyst is supported on the carrier.Carrier can comprise carbon such as acetylene black or graphite, perhaps can comprise the particle of inorganic material such as aluminium oxide, silica, zirconia, titanium oxide.Can use the commercial available catalyst that has been provided on the carrier, perhaps can utilize known method that noble metal is supported on the carrier, not need to explain in detail these known method herein.
In fuel cell system, supply of fuel is given anode and oxidant such as air or oxygen are supplied to negative electrode, thereby by the which generate electricity by electrochemical reaction between anode and the negative electrode.Fuel is oxidized at anode, and oxidant is reduced at negative electrode, thereby produces voltage difference between electrode.
Electrode basement can comprise carbon paper, charcoal cloth, charcoal felt or hardware cloth, but is not limited thereto.Electrode basement support catalyst layer also promotes reacting fluid to be diffused into and enters catalyst layer easily.In order to prevent to use the waterproof electrode basement of handling with the fluoro-based polyalcohol because the gaseous diffusion efficient that the water that produces causes reduces in the operation of fuel cells process.Suitable fluoro-based polyalcohol comprises polyvinylidene fluoride, polytetrafluoroethylene, fluorinated ethylene propylene (FEP), polychlorotrifluoroethylene, and fluoroethylene polymer.
In order to increase the gaseous diffusion effect between electrode basement and the catalyst layer, electrode can also comprise microporous layer.Comprise required conductive powder, adhesive and ionomeric composition by coating, can form microporous layer.Usually, conductive powder can comprise carbon dust, carbon black, acetylene black, active carbon, or nanometer-carbon such as carbon nano-tube, carbon nano-fiber, carbon nanocoils, Carbon Nanohorn, carbon nano ring etc.The limiting examples of adhesive comprises polytetrafluoroethylene (PTFE), polyvinylidene fluoride, the copolymer of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polyvinyl alcohol, and cellulose acetate.
The fuel cell system that comprises membrane-electrode assembly of the present invention comprises at least one generator unit, fuel supply unit and oxidant feeding unit.
Described generator unit comprises membrane-electrode assembly, and is positioned at the dividing plate of these membrane-electrode assembly both sides, negative electrode and anode that described membrane electrode assembly comprises polyelectrolyte film and is positioned at both sides.It generates electricity this generator unit by the reduction of fuel oxidation and oxidant.
Described fuel supply unit is given generator unit with supply of fuel, and the oxidant feeding unit is supplied to generator unit with oxidant.
According to the schematic construction of fuel cell system of the present invention as shown in Figure 2, it only illustrates in many fuel cell systems one.Some this fuel cell system utilizes pump that fuel and/or oxidant are offered generator unit, and other fuel cell system replaces utilizing pump that fuel and/or oxidant are provided with the method that spreads, and the invention is not restricted to any concrete fuel cell system.
With reference to figure 2, fuel cell system 400 comprises battery pack 43, and this battery pack comprises at least one generator unit 40, with the also original electric energy that produces of the oxidant that provides by the fuel oxidation that provided by fuel supply unit 4 with by oxidant feeding unit 5.
According to this embodiment, fuel supply unit is equipped with pressurized fuel holding vessel 9, from it to battery pack 43 fuel supplying.Oxidant is supplied to the oxidant feeding unit 5 of the generator unit 40 of battery pack 43, comprises air pump 13.
Described generator unit 40 comprises the membrane-electrode assembly 51 of the reduction of finishing fuel oxidation and oxidant, and is positioned at these membrane-electrode assembly 51 both sides and the dividing plate (bipolar plates) 53 and 55 of fuel and oxidant is provided to membrane electrode assembly.
The following examples and Comparative Examples are understood the present invention in more detail.Yet, should be appreciated that the present invention is not limited by these embodiment.
Embodiment 1
At room temperature with vacuum in, evaporate commercial available 5wt%NAFION
/ H
2(Solution Technology Inc., EW=1100) solution stirs the O/2-propyl alcohol simultaneously, obtains solid NAFION resin.With the resulting solid NAFION of 5 weight portions
Resin join 100 weight portions dimethylacetylamide (Aldrich, DMAc) in, and, make cation exchange resin liquid (5wt%NAFION 100 ℃ of following mechanical agitation 24 hours
/ DMAc).
Will be based on montmorillonite (the Southern Clay Products that handled with organic modifiers of 2 weight portions of the cation exchange resin of 100 weight portions, Cloisite10A, aspect ratio is 1/500 under the state that organically-modified therein profit is embedded fully, long axis length is about 0.3 μ m), join in the cation exchange resin liquid.Then, under 100 ℃, mix the mixture 24 hours of gained, apply ultrasonic wave simultaneously, thereby obtain cation exchange resin liquid mixture (NAFION by magnetic stirring apparatus (magnet agitator)
/ MMT/DMAc).Make the silicate layering between the montmorillonite layer by the cation exchange resin chain is embedded into, make the cation exchange resin liquid mixture.The silicate interfloor distance of layering is 3nm or bigger.
30cm is installed
2Porousness polytetrafluoroethylene polymer carrier (W.L.Gore, 17mm Gore-Tex, porosity: 80%), and with carbon paper (Toray TGPH-090) adheres to the both sides of carrier.The coating compound of NAFION/MMT/DMAc mixed solutions that will comprise 15 grams is poured on the paper and utilizes roller to repeat coating, and is dry down at 100 ℃ subsequently.This coating and dry run repeat five times, thereby make the polyelectrolyte film that is used for direct oxidation fuel cell that thickness is 25 μ m, and it has porous polymer carrier and hydrocarbon fuel diffusion impervious layer.In coating process, the strained polymer carrier makes thickness be reduced to 15 μ m, and the hydrocarbon fuel diffusion impervious layer is 10 μ m.
In polyelectrolyte film, the weight ratio of cation exchange resin, polymer support and montmorillonite is 100: 13.6: 2.
Respectively with 5wt%NAFION
/ H
2O/2-propanol solution, DPG and deionized water and Pt-Ru are black (in the formula; " deceive " and be meant " catalyst that does not support ", Johnson Matthey, HiSpec 6000) and black (the Johnson Matthey of Pt; HiSpec1000) particle mixes, and makes catalyst pulp.By silk screen printing various slurries are applied to TEFLON
On (polytetrafluoroethylene) film, subsequent drying obtains catalyst layer.Each catalyst layer is positioned on the polyelectrolyte film that makes, and at 200 ℃ and 200kgf/cm
2Pressure under hot compression 3 minutes, thereby obtain that load capacity is 4mg/cm on each side of electrolyte membrane
2Negative electrode and anode.
Layout derives from the ELAT electrode basement (gas diffusion layers) of E-Tek company, make its contact wherein put into the negative electrode and the anode of polyelectrolyte film, and assembling obtains membrane-electrode assembly.
Prepared membrane-electrode assembly is put between the fiberglass blankets of polytetrafluoroethylene coating, then put it between two dividing plates of gas flow with reservation shape and cooling duct, between the copper end plate, compress then, thereby make element cell.Under the condition of 1M methyl alcohol and dry air inflow, the power output of measuring unit battery is with the variation of working temperature then.
Embodiment 2
Prepare polyelectrolyte film according to the method identical with embodiment 1, different is, uses the montmorillonite based on 10 weight portions of the cation exchange resin of 100 weight portions.The weight ratio of cation exchange resin, polymer support and montmorillonite is about 100: 13.6: 2 in prepared polyelectrolyte film, and it is identical with embodiment 1.
Embodiment 3
Prepare polyelectrolyte film according to the method identical with embodiment 1, different is, the cation exchange resin liquid that obtains among kaolinite and the embodiment 1 is mixed, thereby make the cation exchange resin liquid mixture.Cation exchange resin in prepared polyelectrolyte film, polymer support and kaolinic weight ratio are about 100: 13.6: 2.
Embodiment 4
Prepare polyelectrolyte film according to the method identical with embodiment 1, different is the fluorine hectorite to be mixed with the cation exchange resin liquid that obtains in embodiment 1, thereby make the cation exchange resin liquid mixture.The weight ratio of the cation exchange resin in prepared polyelectrolyte film, polymer support and fluorine hectorite is about 100: 13.6: 2.
Prepare polyelectrolyte film according to the method identical with embodiment 1, different is, the NAFION that 130g is obtained at embodiment 1
/ MMT/DMAc cation exchange resin liquid mixture repeats to be coated on the 30 μ m porousness Haloport Fs.The weight ratio of the cation exchange resin in prepared polyelectrolyte film, polymer support and montmorillonite is about 100: 13.6: 2.
Prepare polyelectrolyte film according to the method identical with embodiment 1, difference is as follows.The solid NAFION of embodiment 1 will be derived from
Resin dissolves obtains NAFION in dimethylacetylamide
/ MMT/DMAc solution.Be coated on the 15 μ m porousness Haloport Fs again this solution weight of 45 grams and drying, thereby make the 15 μ m NAFION that do not contain inorganic additive
/ poly tetrafluoroethylene.The NAFION of the 20g of embodiment 1 will be derived from
The coating of/DMAc cation exchange resin liquid mixture is coated on NAFION
The both sides of/poly tetrafluoroethylene, thus make the polyelectrolyte film that does not contain silicate in the intermediate layer.
It is about 100: 13.6: 2 cation exchange resin, polymer support and montmorillonite that prepared polyelectrolyte film comprises weight ratio.
Embodiment 7
Prepare polyelectrolyte film according to the method identical with embodiment 1, difference is as follows.Add respectively based on 4 weight portions of the cation exchange resin of 100 weight portions and the montmorillonite of 2 weight portions, make the first and second cation exchange resin liquid mixtures.This first and second cation exchange resins liquid mixture is coated on the both sides of porousness polytetrafluoroethylene polymer carrier.By the surface and the anode positioned opposite that will scribble the first cation exchange resin liquid mixture, prepare element cell according to the method identical with embodiment 1.It is about 100: 13.6: 2 cation exchange resin, polymer support and montmorillonite that prepared polyelectrolyte film comprises weight ratio.
Embodiment 8
Prepare polyelectrolyte film according to the method identical with embodiment 1, different is, with NAFION
/ MMT/DMAc cation exchange resin liquid mixture directly is coated on the surface that does not have carbon paper.It is about 100: 13.6: 2 cation exchange resin, polymer support and montmorillonite that prepared polyelectrolyte film comprises weight ratio.
Comparative Examples 1
Prepare cation exchange resin liquid mixture (NAFION according to the method identical with embodiment 1
/ MMT/DMAc), the cation exchange resin chain is embedded between the montmorillonite layer so that the silicate layering.By under 110 ℃, liquid mixture being coated on last 12 hour of horizontal glass substrate and evaporating solvent, make the thick NAFION of 30 μ m
/ MMT polyelectrolyte film.Even for the surface that makes prepared polyelectrolyte film, after film being arranged between the thick Kapton film of 50 μ m, under 100 ℃, apply 40 pounds/inch
2Pressure 2 hours.
Comparative Examples 2
With commercial 5wt%NAFION
/ H
2O/2-propyl alcohol (Solution Technology Inc.EW=1100) solution weight is coated on the porousness Haloport F that uses among the thick embodiment 1 of 17 μ m again, makes the thick polyelectrolyte film that does not contain inorganic additive of 25mm.
Comparative Examples 3
Handle the NAFION of the commercial E.I.Dupont of deriving from 100 ℃ the aqueous solution that comprises 3% hydrogen peroxide and 0.5M sulfuric acid
115 films (125 μ m are thick) 1 hour make polyelectrolyte film, and with 100 ℃ deionized water wash 1 hour.
*The measurement of SEM/EDS
Utilize SEM/EDS, carry out the Al-mapping (mapping) of the silicate of the polyelectrolyte film that makes in embodiment 1 and the Comparative Examples 1 is analyzed.The result is shown in respectively among Fig. 3 and Fig. 4.As shown in Figure 4, at the NAFION of the Comparative Examples 1 that makes by general simple solvent evaporation (being the casting film process)
In/MMT the polyelectrolyte film, the sedimentation of inorganic silicate takes place owing to the density contrast between two kinds of materials in solvent evaporation process, inorganic material particle is not dispersed in the electrolyte membrane but is concentrated in lower surface as a result.Do not wish preparation sandwich construction, because resistive component may increase between the electrolyte layer in order to prevent this phenomenon from taking place.On the contrary, as shown in Figure 3, cause inorganic additive to be evenly distributed in the whole cross section of electrolyte membrane by being coated with the embodiment 1 that makes for five times.
*The measurement of ionic conductivity
Utilization derives from the conductivity measurement pond of BekkTech, measures the ionic conductivity according to the electrolyte membrane of embodiment 1 and Comparative Examples 1.Measure according to AC impedance, condition is as follows: the relative humidity of adjusting, frequency are 100Hz～1MHz, and disturbance voltage is 10mV, and have the hydrogen of humidification to flow into electrolyte membrane.Measurement result is as shown in table 1.
Table 1
| Front side (air side) ionic conductivity (S/cm) | Bottom side ionic conductivity (S/cm) | |
| Embodiment 1 | 0.071 | 0.072 |
| Comparative Examples 1 | 0.075 | 0.041 |
| Comparative Examples 3 | 0.084 | 0.084 |
As shown in table 1, the ionic conductivities of measuring in two examples of the electrolyte membrane that makes according to Comparative Examples 1 have conductivity variations between two surfaces, and are uniform according to the both sides conductivity of the electrolyte membrane of embodiment 1.These results show, inorganic additive is evenly distributed in the polyelectrolyte film according to embodiment 1, are distributed in a side of film in Comparative Examples 1 but more.
*Dimensional stability
According to ASTM D570, utilize deionized water and methyl alcohol/deionized water cosolvent, measure the dimensional stability with the polyelectrolyte film of Comparative Examples 1 and 3 according to embodiment 1.In order to estimate dimensional stability, also measured the change in volume of electrolyte membrane with methanol concentration.The results are shown among Fig. 5.As shown in Figure 5, be aggregated that the thing carrier is strengthened and dimensional stability that wherein electrolyte membrane of the embodiment 1 that disperses with nanometer-attitude of inorganic additive has the greatest improvement of obtaining, show to prevent in battery long-term work process the transfer of excessive stress that the expansion owing to electrolyte membrane causes to gas diffusion layers.
*The sealing of polymer support
SEM photo according to the polymer support of embodiment 1 and Comparative Examples 2 is shown in respectively among Fig. 6 and Fig. 7.As shown in Figure 6 and Figure 7, the hole of the void ratio Comparative Examples 2 of polymer support is more effectively sealed by cation exchange resin and silicate in according to the polyelectrolyte film of embodiment 1.
*The BET porosity
In order to estimate the adhesion characteristics between cation exchange resin and the polymer support, measured film BET porosity according to embodiment 1 and Comparative Examples 1 to 3.The results are shown in the table 2.As shown in table 2, because cation exchange resin and inorganic additive, utilization has the cation exchange resin liquid mixture according to embodiment 1 of the organic solvent of high-k, and is better with the liquid mixture according to Comparative Examples 2 of ol-yl solvent coated polymeric carrier to the wetability Billy of height hydrophobic polymer carrier.The wetability improvement causes porosity to reduce.According to mutually combining by force between cation exchange resin and the inorganic additive in the cation exchange resin liquid mixture of embodiment 1, caused than the lower porosity of the commercial electrolyte membrane in the Comparative Examples 3 with for the better barrier properties of methanol fuel.
Table 2
| Porosity (%) | |
| Embodiment 1 | 6.1 |
| Comparative Examples 1 | 8.2 |
| Comparative Examples 2 | 17.2 |
| Comparative Examples 3 | 9.1 |
*Methanol permeability
The methanol permeability of electrolyte membrane is measured as follows: the electrolyte membrane sample is put into discharging pond (two-compartment discharge cell), two chamber, the methyl alcohol/deionized water mixture of 15wt% and deionized water are circulated in discharging pond, two chamber.At this moment, measurement penetrates the methanol concentration of electrolyte membrane according to change of refractive.According to ASTM D882, measured mechanical property.The results are shown in the table 3.
Table 3
| Thickness (μ m) | Methanol permeability (cmcm 3/cm 2Second) | 0.4V power output density (mW/cm 2，60℃) | |
| Embodiment 1 | 25 | 2.7×10 -7 | 80 |
| Embodiment 2 | 25 | 10×10 -7 | 50 |
| Comparative Examples 1 | 30 | 3.5×10 -7 | 68 |
| Comparative Examples 2 | 25 | 3.0×10 -6 | 45 |
| Comparative Examples 3 | 125 | 2.0×10 -6 | 56 |
As shown in table 3, compare with Comparative Examples 2～3, greatly reduce methanol permeability according to the film of embodiment 1 and 2.Particularly, methanol permeability also is lower than the conventional polymer electrolyte membrane that thickness is 130 μ m.Be not bound by theory, think that these results are because as above described with reference to figure 6 and Fig. 7, the void ratio Comparative Examples 2 of polymer support and 3 hole are more effectively sealed in the polyelectrolyte film of embodiment 1.
In table 3, the methanol permeability of embodiment 1 is similar to Comparative Examples 1 among Fig. 8.Yet, because the either side of the electrolyte membrane of conductivity in embodiment 1 all is that so compare with Comparative Examples 1, embodiment 1 has better power of battery output density uniformly.
Fig. 9 illustrates when operation utilizes the fuel cell that the polyelectrolyte film according to embodiment 1 and Comparative Examples 3 makes, and the power output density over time.
Fuel cell is according to following operation: under 60 ℃, be injected in the fuel cell with the 1M methyl alcohol that acts as a fuel with as the air of oxidant and move, and close every day once, simultaneously the humidity and the flow of controlled oxidation agent air.In Fig. 9, this is expressed as ON/OFF scheme numbering.The electrolyte membrane according to embodiment 1 with film resistor (conductivity/thickness), fuel barrier properties and dimensional stability of improvement is with the commercial NAFION in the Comparative Examples 3
115 films are compared, and have better power output stability.
Figure 10 is the transmission electron micrograph according to the electrolyte membrane of embodiment 2.As seen because the cation exchange resin chain is embedded between the inorganic silicate sheet with hierarchy, silicate additive sheet pitch extension is to about 3nm.Confirmed that in order to have the methyl alcohol barrier properties by the layering of cation exchange resin mesosilicic acid salt, the slab organization with normal silicate interfloor distance should break or interfloor distance should be more than or equal to 3nm.Yet, when joining excessive hydrophobic silicic acid salt particle in the cation exchange resin, but having hindered the aquation of cation exchange resin, it causes the conductivity of film to reduce.
By the liquid mixture of cation exchange resin and inorganic additive being injected the hole of porous polymer carrier, make the polyelectrolyte film that is used for direct oxidation fuel cell of the present invention.This film can increase the diffusion admittance of liquid or gaseous hydrocarbon fuel, and has a better barrier properties for hydrocarbon fuel, because the hole of porous carrier can be sealed effectively, and the silicate additive with layer structure and high aspect ratio is dispersed in the polyelectrolyte film with stratification state.Therefore, and utilize porous carrier to have the more conventional film of somewhat complex design to compare, even film, this film also can be used for direct oxidation fuel cell.
Even thickness is reduced to the about 1/5 of conventional film thickness, whole methanol permeabilities of film of the present invention also are less than or equal to the conventional polymer electrolyte membrane (130～180 μ m are thick) that is used for direct oxidation fuel cell.The conductivity that the reduction of this thickness is used in high power fuel cell improves.And because the dimensionally stable property improvement, the electrode/electrolyte interface is more durable.
Although described the present invention in conjunction with exemplary, but should be appreciated that the present invention is not subjected to the restriction of disclosed embodiment, this means that on the contrary the present invention has covered design and various modifications in the scope and the equivalent scheme that is included in appended claims.
Claims (70)
1. polyelectrolyte film that is used for direct oxidation fuel cell comprises:
Define the porous polymer carrier of a lot of holes; And
The hydrocarbon fuel diffusion impervious layer, it is formed on the porous polymer carrier, and comprises the inorganic additive that is scattered in the cation exchange resin.
2. according to the polyelectrolyte film of claim 1, wherein said cation exchange resin and inorganic additive are present in some holes at least.
3. according to the polyelectrolyte film of claim 1, wherein said porous polymer carrier comprises the material that is selected from following: the homopolymers of polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyimides, polybenzoxazole and polybenzimidazoles, and copolymer.
4. according to the polyelectrolyte film of claim 3, wherein this porous polymer carrier comprises the material that is selected from following: polytetrafluoroethylene, polyvinylidene fluoride, and copolymer.
5. according to the polyelectrolyte film of claim 4, wherein said porous polymer carrier comprises the polytetrafluoroethylene homopolymers.
6. according to the polyelectrolyte film of claim 1, the porosity of wherein said porous polymer carrier is at least 80%.
7. according to the polyelectrolyte film of claim 6, the porosity of wherein said porous polymer carrier is 80～90%.
8. according to the polyelectrolyte film of claim 1, wherein said cation exchange resin comprises and contains the fluoropolymer resin that is selected from following cation exchange group in its side chain: sulfonic group, carboxylic acid group, phosphate, phosphonate group and derivative thereof.
9. according to the polyelectrolyte film of claim 1, the ion exchange ratio of wherein said cation exchange resin is 3～33, and its equivalent weight is 700～2000.
10. according to the polyelectrolyte film of claim 1, wherein said cation exchange resin comprises and is selected from following protonically conductive polymer: fluoro-based polyalcohol, benzimidazole-based polyalcohol, polyimides-based polyalcohol, Polyetherimide-based polyalcohol, polyphenylene sulfide-based polyalcohol, polysulfones-based polyalcohol, polyether sulfone-based polyalcohol, polyether-ketone-based polyalcohol, polyethers-ether ketone-based polyalcohol, polyphenylene quinoxaline-based polyalcohol and composition thereof.
11. according to the polyelectrolyte film of claim 10, wherein this cation exchange resin is selected from fluoro-based polyalcohol, polybenzimidazoles-based polyalcohol, polysulfones-based polyalcohol and composition thereof.
12. according to the polyelectrolyte film of claim 1, wherein said inorganic additive is present in the cation exchange resin with the form of the nanophase of layering.
13. according to the polyelectrolyte film of claim 1, wherein said inorganic additive comprises the material that is selected from following: silica, aluminium oxide, zeolite, barium titanate, pottery, inorganic silicate, phosphoric acid hydrogen zirconium, α-Zr (O
A1PCH
A2OH)
a(O
B1PC
B2H
B4SO
B5H)
bNH
2A1, a2, a, b1, b2, b4, b5 and b are that 0～14 identical or different integer and n are 0～50 integer in the O formula, ν-Zr (PO
A1) (H
A2PO
A3)
a(HO
B1PC
B2H
B3SO
B4H)
bNH
2A1, a2, a3, a, b1, b2, b3, b4 and b are that 0～14 identical or different integer and n are 0～50 integer in the O formula, Zr (O
A1PC
A2H
A3)
aY
bA1, a2, a3, a and b are 0～14 identical or different integer in the formula, Zr (O
A1PCH
A2OH)
aY
bNH
2A1, a2, a and b are that 0～14 identical or different integer and n are 0～50 integer in the O formula, α-Zr (O
A1PC
A2H
A3SO
A4H)
aNH
2A1, a2, a3, a4 and a are that 0～14 identical or different integer and n are 0～50 integer in the O formula, α-Zr (O
A1POH) H
2A1 is 0～14 integer in the O formula, (P
2O
5)
a(ZrO
2)
bA and b are 0～14 identical or different integer in the glass type, P
2O
5-ZrO
2-SiO
2Glass, and composition thereof.
14. according to the polyelectrolyte film of claim 13, wherein said inorganic additive is an inorganic silicate.
15. according to the polyelectrolyte film of claim 14, wherein said inorganic silicate is selected from pyrophyllite-talcum, montmorillonite (MMT), fluorine hectorite, kaolinite, vermiculite, illite, mica, clintonite or its mixture.
16. according to the polyelectrolyte film of claim 14, the aspect ratio of wherein said inorganic silicate is 1/30～1/1000.
17. according to the polyelectrolyte film of claim 14, the long axis length of wherein said inorganic silicate is 0.05～0.5 μ m.
18. according to the polyelectrolyte film of claim 14, wherein said inorganic silicate has the structure of layering, and the distance between each silicate layer is at least 3nm.
19. according to the polyelectrolyte film of claim 14, wherein said inorganic silicate is the silicate of handling with organic modifiers.
20. according to the polyelectrolyte film of claim 19, wherein said organic modifiers comprises at least a following compound: the C that is selected from
1～C
20Alkylamine, C
1～C
20Alkylenediamine, C
1～C
20Quaternary ammonium salt, aminohexane and nitrogenous heterocyclic compound.
21. according to the polyelectrolyte film of claim 1, the amount of wherein said cation exchange resin is 50～90 weight %, the amount of described porous polymer carrier is 2～30 weight %, and the amount of described inorganic additive is 0.5～20 weight %.
22. according to the polyelectrolyte film of claim 21, the amount of wherein said cation exchange resin is 70～80 weight %, the amount of described porous polymer carrier is 2～15 weight %, and the amount of described inorganic additive is 0.5～10 weight %.
23. according to the polyelectrolyte film of claim 1, wherein said hydrocarbon fuel diffusion impervious layer also comprises and has low-molecular-weight acrylate-based polyalcohol.
24. according to the polyelectrolyte film of claim 1, wherein said hydrocarbon fuel diffusion impervious layer also comprises by the cation exchange resin of 100 weight portions counts 5～10 parts by weight of acrylic ester-based polyalcohols.
25. according to the polyelectrolyte film of claim 1, the thickness of wherein said porous polymer carrier is 10～15 μ m.
26. according to the polyelectrolyte film of claim 1, the thickness of wherein said hydrocarbon fuel diffusion impervious layer is 2～10 μ m.
27. according to the polyelectrolyte film of claim 1, wherein the thickness of this polyelectrolyte film is 5～100 μ m.
28. according to the polyelectrolyte film of claim 1, wherein said polyelectrolyte film one side and be formed with electric conductivity difference between the opposite side of catalyst layer on it less than 5%.
29. according to the polyelectrolyte film of claim 1, wherein the porosity of this polyelectrolyte film is 1～10%.
30. a method for preparing the polyelectrolyte film of direct oxidation fuel cell comprises:
The cation exchange resin that side chain is had cation exchange group is dissolved in first organic solvent, makes cation exchange resin liquid;
By mixing this cation exchange resin liquid and solid phase or liquid phase inorganic additive, obtain mixed solution; And
Described mixed solution is coated on the porous polymer carrier, makes polyelectrolyte film.
31. according to the method for claim 30, wherein said first organic solvent is selected from: N-N-methyl-2-2-pyrrolidone N-(NMP), dimethyl formamide (DMF), dimethylacetylamide (DMA), oxolane (THF), methyl-sulfoxide (DMSO), acetone, methylethylketone (MEK), tetramethylurea, trimethyl phosphate, butyrolactone, isophorone, carbitol acetate, methylisobutylketone, N-butylacetic acid ester, cyclohexanone, diacetone alcohol, isobutyrone, ethyl acetoacetate, glycol ether, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and composition thereof.
32. according to the method for claim 30, wherein said inorganic additive comprises and is selected from following compound: silica, aluminium oxide, zeolite, barium titanate, pottery, inorganic silicate, phosphoric acid hydrogen zirconium, α-Zr (O
A1PCH
A2OH)
a(O
B1PC
B2H
B4SO
B5H)
bNH
2A1, a2, a, b1, b2, b4, b5 and b are that 0～14 identical or different integer and n are 0～50 integer in the O formula, ν-Zr (PO
A1) (H
A2PO
A3)
a(HO
B1PC
B2H
B3SO
B4H)
bNH
2A1, a2, a3, a, b1, b2, b3, b4 and b are that 0～14 identical or different integer and n are 0～50 integer in the O formula, Zr (O
A1PC
A2H
A3)
aY
bA1, a2, a3, a and b are 0～14 identical or different integer in the formula, Zr (O
A1PCH
A2OH)
aY
bNH
2A1, a2, a and b are that 0～14 identical or different integer and n are 0～50 integer in the O formula, α-Zr (O
A1PC
A2H
A3SO
A4H)
aNH
2A1, a2, a3, a4 and a are that 0～14 identical or different integer and n are 0～50 integer in the O formula, α-Zr (O
A1POH) H
2A1 is 0～14 integer in the O formula, (P
2O
5)
a(ZrO
2)
bA and b are 0～14 identical or different integer in the glass type, P
2O
5-ZrO
2-SiO
2Glass, and composition thereof.
33. according to the method for claim 32, wherein said inorganic additive is an inorganic silicate.
34. according to the method for claim 33, wherein said inorganic silicate is the silicate of handling with organic modifiers.
35. according to the method for claim 34, wherein said organic modifiers is selected from: C
1～C
20Alkylamine, C
1～C
20Alkylenediamine, C
1～C
20Quaternary ammonium salt, aminohexane and nitrogenous heterocyclic compound.
36. according to the method for claim 30, wherein said inorganic additive is the liquid inorganic additive that makes in second organic solvent by inorganic additive is joined.
37. according to the method for claim 36, wherein said second organic solvent is selected from: the 1-propyl alcohol, the 2-propyl alcohol, and composition thereof.
38. according to the method for claim 30, wherein said inorganic additive mixes with cation exchange resin liquid by the amount that 100 weight portion cation exchange resin liquid are counted 0.5～10 weight portion.
39. according to the method for claim 30, wherein said mixed solution also comprises and has low-molecular-weight acrylate-based polyalcohol.
40. according to the method for claim 30, wherein said mixed solution is the amount adding of 5～10 weight portions by 100 weight portion cation exchange resins.
41. the fuel cell system of a direct oxidation comprises:
-at least one generator unit, it is by the also original generating of fuel oxidation and oxidant, and and draw together:
Membrane-electrode assembly, this membrane electrode assembly comprise polyelectrolyte film and are arranged in the negative electrode and the anode of these polyelectrolyte film both sides, reach
Be positioned at the dividing plate of described membrane electrode assembly both sides;
-with the fuel supply unit of supply of fuel to generator unit; And
-oxidant is supplied to the oxidant feeding unit of generator unit,
Wherein said polyelectrolyte film comprises:
Define the porous polymer carrier of a lot of holes; And
The hydrocarbon fuel diffusion impervious layer, it is formed on the described polymer support, and comprises the inorganic additive that is scattered in the cation exchange resin.
42. according to the fuel cell system of claim 41, wherein said cation exchange resin and inorganic additive are present in the described hole.
43. fuel cell system according to claim 41, wherein said porous polymer carrier comprises and is selected from following material: polytetrafluoroethylene, the homopolymers of polyvinylidene fluoride, polyethylene, polypropylene, polyimides, polybenzoxazole, polybenzimidazoles, and copolymer.
44. according to the fuel cell system of claim 43, wherein said porous polymer carrier comprises and is selected from following material: polytetrafluoroethylene, polyvinylidene fluoride, and copolymer.
45. according to the fuel cell system of claim 44, wherein said porous polymer carrier comprises the polytetrafluoroethylene homopolymers.
46. according to the fuel cell system of claim 41, the porosity of wherein said porous polymer carrier is at least 80%.
47. according to the fuel cell system of claim 46, the porosity of wherein said porous polymer carrier is 80～90%.
48. according to the fuel cell system of claim 41, wherein said cation exchange resin comprises that its side chain contains the fluoropolymer resin that is selected from following cation exchange group: sulfonic group, carboxylic acid group, phosphate, phosphonate group and derivative thereof.
49. according to the fuel cell system of claim 41, the ion exchange ratio of wherein said cation exchange resin is 3～33, and its equivalent weight is 700～2000.
50. according to the fuel cell system of claim 41, wherein said cation exchange resin comprises at least a following protonically conductive polymer that is selected from: fluoro-based polyalcohol, benzimidazole-based polyalcohol, polyimides-based polyalcohol, Polyetherimide-based polyalcohol, polyphenylene sulfide-based polyalcohol, polysulfones-based polyalcohol, polyether sulfone-based polyalcohol, polyether-ketone-based polyalcohol, polyethers-ether ketone-based polyalcohol and polyphenylene quinoxaline-based polyalcohol.
51. according to the fuel cell system of claim 50, wherein said cation exchange resin comprises and is selected from following material: fluoro-based polyalcohol, polybenzimidazoles-based polyalcohol, polysulfones-based polyalcohol and composition thereof.
52. according to the fuel cell system of claim 41, wherein said inorganic additive is present in the cation exchange resin with the form of the nanophase of layering.
53. according to the fuel cell system of claim 41, wherein said inorganic additive comprises and is selected from following compound: silica, aluminium oxide, zeolite, barium titanate, pottery, inorganic silicate, phosphoric acid hydrogen zirconium, α-Zr (O
A1PCH
A2OH)
a(O
B1PC
B2H
B4SO
B5H)
bNH
2A1, a2, a, b1, b2, b4, b5 and b are that 0～14 identical or different integer and n are 0～50 integer in the O formula, ν-Zr (PO
A1) (H
A2PO
A3)
a(HO
B1PC
B2H
B3SO
B4H)
bNH
2A1, a2, a3, a, b1, b2, b3, b4 and b are that 0～14 identical or different integer and n are 0～50 integer in the O formula, Zr (O
A1PC
A2H
A3)
aY
bA1, a2, a3, a and b are 0～14 identical or different integer in the formula, Zr (O
A1PCH
A2OH)
aY
bNH
2A1, a2, a and b are that 0～14 identical or different integer and n are 0～50 integer in the O formula, α-Zr (O
A1PC
A2H
A3SO
A4H)
aNH
2A1, a2, a3, a4 and a are that 0～14 identical or different integer and n are 0～50 integer in the O formula, α-Zr (O
A1POH) H
2A1 is 0～14 integer in the O formula, (P
2O
5)
a(ZrO
2)
bA and b are 0～14 identical or different integer in the glass type, P
2O
5-ZrO
2-SiO
2Glass, and composition thereof.
54. according to the fuel cell system of claim 53, wherein said inorganic additive comprises inorganic silicate.
55. according to the fuel cell system of claim 55, wherein said inorganic silicate is selected from pyrophyllite-talcum, montmorillonite (MMT), fluorine hectorite, kaolinite, vermiculite, illite, mica, clintonite and composition thereof.
56. according to the fuel cell system of claim 54, the aspect ratio of wherein said inorganic silicate is 1/30～1/1000.
57. according to the fuel cell system of claim 54, the long axis length of wherein said inorganic silicate is 0.05～0.5 μ m.
58. according to the fuel cell system of claim 54, wherein said inorganic silicate has the structure of layering, and the distance between each silicate layer is at least 3nm.
59. according to the fuel cell system of claim 54, wherein said inorganic silicate is the silicate of handling with organic modifiers.
60. according to the fuel cell system of claim 59, wherein said organic modifiers comprises and is selected from following compound: C
1～C
20Alkylamine, C
1～C
20Alkylenediamine, C
1～C
20Quaternary ammonium salt, aminohexane, nitrogenous heterocyclic compound and composition thereof.
61. according to the fuel cell system of claim 41, the amount of wherein said cation exchange resin is 50～90 weight %, the amount of described porous polymer carrier is 2～30 weight %, and the amount of described inorganic additive is 0.5～20 weight %.
62. according to the fuel cell system of claim 61, the amount of wherein said cation exchange resin is 70～80 weight %, the amount of described porous polymer carrier is 2～15 weight %, and the amount of described inorganic additive is 0.5～10 weight %.
63. according to the fuel cell system of claim 41, wherein said hydrocarbon fuel diffusion impervious layer also comprises and has low-molecular-weight acrylate-based polyalcohol.
64. according to the fuel cell system of claim 41, wherein said hydrocarbon fuel diffusion impervious layer also comprises by 100 weight portion cation exchange resins counts 5～10 parts by weight of acrylic ester-based polyalcohols.
65. according to the fuel cell system of claim 41, the thickness of wherein said porous polymer carrier is 10～15 μ m.
66. according to the fuel cell system of claim 41, the thickness of wherein said hydrocarbon fuel diffusion impervious layer is 2～10 μ m.
67. according to the fuel cell system of claim 41, the thickness of wherein said polyelectrolyte film is 5～100 μ m.
68. according to the fuel cell system of claim 41, wherein said polyelectrolyte film one side and be formed with electric conductivity difference between the opposite side of catalyst layer on it less than 5%.
69. according to the fuel cell system of claim 41, the porosity of wherein said polyelectrolyte film is 1～10%.
70. a membrane electrode assembly, it comprises the anode and the negative electrode of the polyelectrolyte film both sides that are positioned at claim 1.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR82155/04 | 2004-10-14 | ||
| KR20040082155 | 2004-10-14 | ||
| KR55834/05 | 2005-06-27 | ||
| KR1020050055834A KR100684730B1 (en) | 2004-10-14 | 2005-06-27 | Polymer electrolyte for direct oxidation fuel cell, method of preparing same and direct oxidation fuel cell comprising same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1764001A true CN1764001A (en) | 2006-04-26 |
| CN1764001B CN1764001B (en) | 2010-05-05 |
Family
ID=36748012
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005101137233A Expired - Fee Related CN1764001B (en) | 2004-10-14 | 2005-10-14 | Polymer electrolyte for a direct oxidation fuel cell, method of preparing the same, and direct oxidation fuel cell comprising the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5830386B2 (en) |
| KR (1) | KR100684730B1 (en) |
| CN (1) | CN1764001B (en) |
| DE (1) | DE602005009304D1 (en) |
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| CN106981675A (en) * | 2017-04-10 | 2017-07-25 | 杭州电子科技大学 | It is a kind of for single part of fuel cell and preparation method thereof |
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| DE602006008536D1 (en) * | 2005-06-28 | 2009-10-01 | Samsung Sdi Co Ltd | Polymer electrolyte membrane and membrane electrode assembly for a fuel cell system containing these |
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-
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- 2005-06-27 KR KR1020050055834A patent/KR100684730B1/en not_active IP Right Cessation
- 2005-10-14 CN CN2005101137233A patent/CN1764001B/en not_active Expired - Fee Related
- 2005-10-14 DE DE602005009304T patent/DE602005009304D1/en active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| KR100684730B1 (en) | 2007-02-20 |
| JP2012069536A (en) | 2012-04-05 |
| KR20060048562A (en) | 2006-05-18 |
| DE602005009304D1 (en) | 2008-10-09 |
| JP5830386B2 (en) | 2015-12-09 |
| CN1764001B (en) | 2010-05-05 |
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